CN111518318A - Starch-based biological latex and preparation method and application thereof - Google Patents
Starch-based biological latex and preparation method and application thereof Download PDFInfo
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- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention provides a starch-based biological latex and a preparation method and application thereof, wherein the starch-based biological latex has a solid content of 45-55% and comprises the following raw materials in parts by mass: the absolute dry mass percentage of the starch is 100 percent; the mass percentage of the starch cross-linking agent to the absolutely dry starch is 5-15%; the mass percentage of the starch plasticity transforming agent to the absolutely dry starch is 7-20%; adding water at normal temperature according to the solid content of the starch-based biological latex; wherein, the content of water in the starch is less than or equal to 15 percent, the solid contents of the starch cross-linking agent and the starch plastic transforming agent are both 50 +/-2 percent, and the proper type of the starch cross-linking agent and the starch plastic transforming agent with matched types are selected to improve the plasticity of the starch so as to control the chain length and the modification of the starch, thereby improving the bending elasticity and the strength and the water resistance of the starch after film forming; in the process of adding water, heating and boiling in the preparation kettle, proper reaction temperature and time are controlled, so that the reaction becomes simple and efficient.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a coating technology in papermaking, in particular to a starch-based biological latex and a preparation method and application thereof.
[ background of the invention ]
In recent years, the price of products using petroleum products as raw materials is increasing, and in addition, petroleum products can cause environmental pollution, so in many petroleum product industries, especially in the paper making industry, more and more enterprises are dedicated to search for low-price, regenerated and pollution-free environment-friendly adhesive raw materials to replace traditional petroleum cracking products, such as petroleum-based latex synthesized by using butadiene and styrene as main monomers, for example, carboxylated styrene-butadiene latex. Moreover, starch is an organic compound with abundant natural content, has the remarkable characteristics of wide source, low price, degradability, renewability and the like, can be used as biological latex after being subjected to related modification treatment, and can partially or completely replace petroleum-based latex. The coating of the paper mill coated paper mainly comprises pigment, adhesive and auxiliary agent, the cost is mainly influenced by latex, calcium and starch, and in order to reduce the production cost and meet the requirement of environmental protection, the paper mill uses partial biological latex to replace carboxylic styrene-butadiene latex as the adhesive for coating the pigment.
In the existing paper coating process, the biological latex is mainly prepared by adding a starch modifier into a starch raw material, heating to a high temperature, preserving heat for a period of time, for example, heating to a high temperature of 80-95 ℃, preserving heat for 30-60 min, adding a catalyst, oxidizing for 30-120 min, adjusting the pH value, adding a crosslinking agent, reacting for 20-90 min at 50-70 ℃, and finally performing cooling screening and other technological measures; or adding some buffer solution into the starch solution, mixing, heating to 50-60 ℃, stirring, preserving heat for 40-60min, adding amylase, adjusting the pH value, reacting for 30-60 min, performing a series of drying, adding some organic solvent, dissolving, preserving heat for 60-180 min and the like to obtain the biological latex. In the above process, the selected auxiliary agent or amylase has higher requirements on reaction conditions, and the required processing effect can be achieved only by controlling the pH value within a certain range and carrying out longer reaction time and higher reaction temperature, so that the whole reaction process is long and the reaction temperature is high; moreover, the addition of various additives reaches three, four or more, which causes the operation process of the whole preparation process to be more complicated; meanwhile, the preparation process is selective to starch, is only suitable for single native starch or modified (denatured) starch, and once the process is shaped, the raw materials cannot be changed.
[ summary of the invention ]
Aiming at the problems that the reaction is complex due to excessive reaction auxiliary agents selected at present, the reaction temperature and the reaction time are further influenced, or the efficiency of selected reaction enzymes or auxiliary agents is not high, the invention provides the starch-based biological latex, which has the advantages that the starch raw materials are not limited, the reaction conditions and the reaction equipment are simple, one or two efficient reaction auxiliary agents are adopted to replace various auxiliary agents, the equipment flow is simplified, the chemical reaction in the preparation process is simple and efficient, the preparation process time is short, and the efficiency is high, and the preparation method and the application thereof.
In order to achieve the purpose, the technical scheme is as follows:
a starch-based biological latex has a target solid content of 45-55%, and comprises the following raw materials in parts by mass:
starch, the absolute dry mass percentage is 100%;
the starch cross-linking agent accounts for 5-15% of the mass percentage of the absolutely dry starch;
the starch plasticity transforming agent accounts for 7-20% of the weight percentage of the absolutely dry starch;
adding water with the normal temperature water in an amount which is 45-55% of the target solid content designed according to the starch-based biological latex;
wherein, the content of water in the starch raw material is less than or equal to 15 percent, and the solid contents of the starch cross-linking agent and the starch plastic transforming agent are both 50 +/-2 percent.
Further, the starch is one or more than two of cassava native starch, corn native starch, modified cassava starch and modified corn starch; the modified tapioca starch is obtained by chemically modifying tapioca, and the modified corn starch is obtained by chemically modifying corn native starch.
Further, the starch cross-linking agent is a polyamide polyurea resin starch cross-linking agent.
Further, the starch plasticity converting agent is an N, N-dihydroxyethylformamide starch plasticity converting agent.
Further, the starch-based biological latex is a light yellow transparent liquid, the solid content is 45-55%, the viscosity at the temperature of 25 ℃ is 150-500 mpa.s, and the pH value is 6-7.
A preparation method of starch-based biological latex comprises the following steps:
(1) equipment preparation
A reaction kettle, a metering pump and a storage tank with functions of stirring and heating by introducing steam;
(2) and preparation treatment
Before preparing the biological latex, firstly setting the preparation pot volume required by a reaction kettle to be 50-100%, and then calculating the total amount of all materials required by preparation according to the target solid content of the biological latex of 45-55%: the starch absolute dry mass fraction is 100%, the polyamide polyurea resin starch crosslinking agent is 5-15% relative to the absolute dry starch mass percentage, and the N, N-dihydroxyethylformamide starch plastic conversion agent is 7-20% relative to the absolute dry starch mass percentage; the insufficient pot capacity of the reaction kettle is the supplementary normal temperature water quantity; wherein the starch is one or more than two of cassava native starch, corn native starch, modified cassava starch and modified corn starch, the content of water in the starch raw material is less than or equal to 15 percent, and the solid contents of the starch cross-linking agent and the starch plastic conversion agent are both 50 +/-2 percent;
during preparation, adding the required supplementary normal-temperature water into a preparation kettle, starting a stirrer, stirring at a low speed of 100-500 rpm, and adding 100% of starch raw materials in absolute dry parts by mass; continuously stirring after the starch raw material is added, starting steam heating of the reaction kettle, heating to 90-95 ℃, turning off the steam, and stirring for 20-25 min; then, adding 5-15% of polyamide polyurea resin starch cross-linking agent in an oven-dry mass fraction relative to the oven-dry starch in percentage by mass, continuously stirring for 10-15 min, adding 7-20% of N, N-dihydroxyethyl formamide starch plastic converting agent in an oven-dry mass fraction relative to the oven-dry starch in percentage by mass, and stirring for 10-15 min to obtain the biological latex which is a light yellow transparent liquid, has a solid content of 45-55%, has a viscosity of 150-500 mpa.s at a temperature of 25 ℃ and has a pH value of 6-7.
Further, in the step (2), after the starch raw material is added, stirring is continued, steam heating of the reaction kettle is started, the temperature is increased to 90-95 ℃, the steam can be turned off, and stirring is carried out for more than 20 min.
Further, in the step (2), 5-15% of polyamide polyurea resin starch cross-linking agent in parts by weight of oven dry is added relative to the oven dry starch in percentage by weight, and the mixture is continuously stirred for more than 10 min.
Further, in the step (2), adding 7-20% of N, N-dihydroxyethyl formamide starch plastic conversion agent in absolute dry mass percentage relative to absolute dry starch, and stirring for more than 10 min.
Use of a starch-based bio-latex for the manufacture of paper.
The invention has the advantages that:
by analyzing the preparation process of the biological latex in various paper mills or chemical plants at present, the reasons for influencing the reaction temperature and the reaction time are that too much reaction auxiliary agent is selected to cause the reaction to be complicated, or the efficiency of the selected reaction enzyme or auxiliary agent is not high. The invention selects one or two high-efficiency reaction auxiliary agents to replace various auxiliary agents, and simplifies the equipment flow, thereby simplifying and improving the chemical reaction process in the preparation process.
In the specific implementation, different types of starch are used as raw materials, and a polyamide polyurea resin starch cross-linking agent is used for performing cross-linking reaction on starch branched chains, so that a bond bridge is formed between one starch molecule and another molecule to generate a cross-linked structure, and the film forming strength and the water resistance of the starch are improved; adding an N, N-dihydroxyethyl formamide starch plasticity conversion agent to improve the plasticity of the starch so as to control the chain length and modification of the starch, thereby improving the bending elasticity and strength of the starch after film forming; the reaction is simple and efficient by selecting a proper type of starch cross-linking agent and a type-matched starch plastic conversion agent.
In addition, in the process of adding water into a preparation kettle, raising the temperature and boiling, proper reaction temperature and time are controlled, so that starch is plasticized, and aggregate particles are completely dispersed into biological latex dispersion liquid with high specific surface area and binding capacity.
In addition, in the whole preparation process, firstly, the starch raw material is not limited, and can be various plant native starches such as corn starch, cassava starch and the like, and can also be various modified starches such as oxidized starch, modified starch, phosphate starch and the like, so that the wide selection range of materials is realized, and only different adding amount ratios of the starch crosslinking agent and the starch plasticity conversion agent are required to be adjusted according to different starch raw materials; secondly, the reaction conditions and reaction equipment are simple, the reaction conditions are loose, the heating can be stopped when the normal pressure and the cooking temperature are raised to 90-95 ℃ without adjusting the pH value, the continuous heat preservation at the temperature of more than 90 ℃ is not needed, and the related operation can be realized only by a reaction kettle with a stirrer; moreover, the preparation process is short in time and high in efficiency, only 2 reaction auxiliary agents are needed to be added, the operation is simple, the whole preparation process is less than 60min, and the actual reaction time is only about 40 min.
[ detailed description ] embodiments
The present invention will be further described with reference to the following specific examples.
Example one
1000kg of starch-based biological latex is prepared from modified cassava starch, water, a polyamide polyurea resin starch cross-linking agent with 50% of solid content and the model LC-6500, and an N, N-dihydroxyethyl formamide starch plastic conversion agent with 50% of solid content and the model FI-550, wherein the content of water in the modified cassava starch is less than or equal to 15%.
Preparing starch solution according to the mass percent, adding 447.6kg of water into a reaction kettle, starting stirring, controlling the rotating speed to be 300rpm, then adding 458.8kg of modified cassava starch to prepare the starch solution, heating to 90 ℃, stopping steam heating and preserving heat for 20min, adding LC-650039kg of polyamide polyurea resin starch cross-linking agent, wherein the mass percent ratio of the modified cassava starch relative to the absolute dry modified cassava starch is 5%; then, stirring for 10min, and adding 7% of an N, N-dihydroxyethylformamide starch plastic conversion agent FI-55054.6kg in mass percent relative to the oven-dried modified cassava starch; and finally, stirring for more than 10min to obtain the required biological latex.
Sampling and detecting product indexes: the biolatex in this example was a pale yellow transparent liquid with a solids content of 50.6%, a viscosity of 480mpa.s, and a pH of 6.7.
Example two
The starch-based biological latex is prepared by 1000kg of cassava native starch, water, a polyamide polyurea resin starch cross-linking agent with 50% of solid content and the model LC-6500, and an N, N-dihydroxyethyl formamide starch plastic conversion agent with 50% of solid content and the model FI-550, wherein the content of water in the cassava native starch is less than or equal to 15%.
Preparing starch solution according to the mass percent, adding 455.2kg of water into a reaction kettle, starting stirring, controlling the rotating speed to be 500rpm, then adding 325kg of cassava native starch to prepare starch solution, heating to 95 ℃, stopping steam heating and preserving heat for 22min, adding LC-650065 kg of polyamide polyurea resin starch cross-linking agent, wherein the mass percent of the polyamide polyurea resin starch cross-linking agent relative to the absolutely dry cassava native starch is 10%; then, stirring for 10min, and adding 15 percent of an N, N-dihydroxyethyl formamide starch plastic conversion agent FI-55097.5 kg in mass percent relative to the absolute dry cassava raw starch; and finally, stirring for more than 10min to obtain the required biological latex.
Sampling and detecting product indexes: the biolatex in this example was a pale yellow transparent liquid with a solids content of 45.7%, a viscosity of 157mpa.s, and a pH of 6.3.
EXAMPLE III
The starch-based biological latex is prepared by 1000kg of corn native starch, water, a polyamide polyurea resin starch cross-linking agent with 50% of solid content and the model of LC-6500, and an N, N-dihydroxyethyl formamide starch plastic converting agent with 50% of solid content and the model of FI-550, wherein the content of water in the corn native starch is less than or equal to 15%.
Preparing starch solution according to the mass percent, adding 333.9kg of water into a reaction kettle, starting stirring, controlling the rotating speed to be 300rpm, then adding 417.7kg of corn native starch to prepare the starch solution, heating to 95 ℃, stopping steam heating and preserving heat for 22min, adding LC-6500106.5 kg of polyamide polyurea resin starch cross-linking agent, wherein the mass percent of the polyamide polyurea resin starch cross-linking agent relative to the absolute dry corn native starch is 15%; then, stirring for 10min, and adding 20 percent of N, N-dihydroxyethyl formamide starch plastic transforming agent FI-550142kg in mass percent relative to the absolute dry corn native starch; and finally, stirring for more than 10min to obtain the required biological latex.
Sampling and detecting product indexes: the biolatex in this example was a pale yellow transparent liquid with a solids content of 54.9%, a viscosity of 266mpa.s, and a pH of 6.6.
The biological latex obtained in the first embodiment, the second embodiment and the third embodiment of the invention respectively replaces the carboxylic styrene-butadiene latex with 10 percent and 30 percent to prepare the coating, and the biological latex and the pure carboxylic styrene-butadiene latex formula coating are subjected to a paper coating performance comparison test to verify the influence on the coating performance.
The quality indexes of the prepared coating are as follows:
as can be seen from the table above, the biological latex obtained in each example is used for preparing the coating by replacing the carboxylic styrene-butadiene latex with 10 percent, and the quality index of the coating is similar to that of a pure carboxylic styrene-butadiene latex formula coating; the coating prepared by 30 percent of the carboxylic styrene-butadiene latex is slightly higher than the viscosity of the pure carboxylic styrene-butadiene latex formula coating, but still belongs to the viscosity range in which paper can be normally coated.
The coating is used for coating paper, and the quality detection indexes are as follows:
as can be seen from the above table, after paper is coated with the coating prepared from the biological latex obtained in each example, the printing gloss, ink transfer amount, dry picking strength, wet strength and the like of the paper are all similar to the quality indexes of the paper coated with the pure carboxylic styrene-butadiene latex formula coating, and therefore, the biological latex prepared by the invention can be considered to be completely used for replacing 10-30% of the carboxylic styrene-butadiene latex in the paper coating.
In summary, in the whole preparation process, firstly, the starch raw material is not limited, and may be various plant native starches such as corn starch, tapioca starch and the like, or modified starches such as oxidized starch, modified starch, phosphate starch and the like obtained by chemically modifying tapioca or corn starch in various ways, because the native starch is influenced by various factors such as plant type sources, seasons, production places and the like, and the direct connection and the branched chain content, the polymerization degree and the like of native starches of different types or different batches are different, so that the quality difference of the native starch is caused; after modification, the differences and the like can be controlled in a relatively stable range, so that the quality of the modified starch of the same type and different batches is relatively stable, the wide selection range of materials is realized, and the different adding amount ratios of the starch crosslinking agent and the starch plastic conversion agent are adjusted according to different starch raw materials; secondly, the reaction conditions and reaction equipment are simple, the reaction conditions are loose, the heating can be stopped when the normal pressure and the cooking temperature are raised to 90-95 ℃ without adjusting the pH value, the continuous heat preservation at the temperature of more than 90 ℃ is not needed, and the related operation can be realized only by a reaction kettle with a stirrer; moreover, the preparation process is short in time and high in efficiency, only 2 reaction auxiliary agents are needed to be added, the operation is simple, the whole preparation process is less than 60min, and the actual reaction time is only about 40 min.
The invention adopts different types of starch as raw materials, utilizes the polyamide polyurea resin starch cross-linking agent to perform cross-linking reaction on starch branched chains, promotes one starch molecule to form a bond bridge with another molecule to generate a cross-linked structure, and improves the film-forming strength and the water resistance of the starch; adding an N, N-dihydroxyethyl formamide starch plasticity conversion agent to improve the plasticity of the starch so as to control the chain length and modification of the starch, thereby improving the bending elasticity and strength of the starch after film forming; by selecting a proper type of starch cross-linking agent and a type-matched starch plastic conversion agent, the reaction becomes simple and efficient. And in the process of adding water into the preparation kettle, heating and decocting, controlling proper reaction temperature and time to plasticize starch, and completely dispersing the aggregate particles into the biological latex dispersion liquid with high specific surface area and binding capacity.
The above-mentioned embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, except for the cases listed in the specific embodiments; all equivalent variations of the methods and principles of the present invention are intended to be within the scope of the present invention.
Claims (10)
1. The starch-based biological latex is characterized in that the target solid content of the starch-based biological latex is 45-55%, and the starch-based biological latex comprises the following raw materials in parts by mass:
starch, the absolute dry mass percentage is 100%;
the starch cross-linking agent accounts for 5-15% of the mass percentage of the absolutely dry starch;
the starch plasticity transforming agent accounts for 7-20% of the weight percentage of the absolutely dry starch;
adding water with the normal temperature water in an amount which is 45-55% of the target solid content designed according to the starch-based biological latex;
wherein, the content of water in the starch raw material is less than or equal to 15 percent, and the solid contents of the starch cross-linking agent and the starch plastic transforming agent are both 50 +/-2 percent.
2. The starch-based biological latex according to claim 1, wherein the starch is one or more of tapioca native starch, corn native starch, modified tapioca starch and modified corn starch.
3. The starch-based biological latex according to claim 1, wherein said starch crosslinking agent is a polyamide polyurea resin starch crosslinking agent.
4. The starch-based biological latex according to claim 1, wherein said starch plasticity transforming agent is N, N-dihydroxyethylformamide starch plasticity transforming agent.
5. The starch-based biological latex according to claim 1, wherein the starch-based biological latex is a light yellow transparent liquid, has a solid content of 45-55%, a viscosity of 150-500 mpa.s at 25 ℃, and a pH value of 6-7.
6. The method for preparing a starch-based biological latex according to any one of claims 1 to 5, comprising the steps of:
(1) equipment preparation
A reaction kettle, a metering pump and a storage tank with functions of stirring and heating by introducing steam;
(2) and preparation treatment
Before preparing the biological latex, firstly setting the preparation pot volume required by a reaction kettle to be 50-100%, and then calculating the total amount of all materials required by preparation according to the target solid content of the biological latex of 45-55%: the starch absolute dry mass fraction is 100%, the polyamide polyurea resin starch crosslinking agent is 5-15% relative to the absolute dry starch mass percentage, and the N, N-dihydroxyethylformamide starch plastic conversion agent is 7-20% relative to the absolute dry starch mass percentage; the insufficient pot capacity of the reaction kettle is the supplementary normal temperature water quantity; wherein the starch is one or more than two of cassava native starch, corn native starch, modified cassava starch and modified corn starch, the content of water in the starch raw material is less than or equal to 15 percent, and the solid contents of the starch cross-linking agent and the starch plastic conversion agent are both 50 +/-2 percent;
during preparation, adding the required supplementary normal-temperature water into a preparation kettle, starting a stirrer, stirring at a low speed of 100-500 rpm, and adding 100% of starch raw materials in absolute dry parts by mass; continuously stirring after the starch raw material is added, starting steam heating of the reaction kettle, heating to 90-95 ℃, turning off the steam, and stirring for 20-25 min; then, adding 5-15% of polyamide polyurea resin starch cross-linking agent in an oven-dry mass fraction relative to the oven-dry starch in percentage by mass, continuously stirring for 10-15 min, adding 7-20% of N, N-dihydroxyethyl formamide starch plastic converting agent in an oven-dry mass fraction relative to the oven-dry starch in percentage by mass, and stirring for 10-15 min to obtain the biological latex which is a light yellow transparent liquid, has a solid content of 45-55%, has a viscosity of 150-500 mpa.s at a temperature of 25 ℃ and has a pH value of 6-7.
7. The preparation method of the starch-based biological latex as claimed in claim 6, wherein in the step (2), the starch raw material is continuously stirred after being added, steam heating of the reaction kettle is started, the steam can be stopped when the temperature is raised to 90-95 ℃, and the stirring is carried out for more than 20 min.
8. The preparation method of the starch-based biological latex as claimed in claim 6, wherein in the step (2), 5-15% of the polyamide polyurea resin starch crosslinking agent is added in a ratio of oven dry weight to oven dry weight of starch, and the mixture is continuously stirred for more than 10 min.
9. The preparation method of the starch-based biological latex as claimed in claim 6, wherein in the step (2), the starch plasticity conversion agent of N, N-dihydroxyethylformamide is added in an amount of 7-20% by mass relative to the absolute dry starch, and the mixture is stirred for more than 10 min.
10. Use of a starch-based bio-latex according to any of claims 1 to 5, wherein said starch-based bio-latex is used in papermaking.
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| CN113215830A (en) * | 2021-04-22 | 2021-08-06 | 杭州纸友科技有限公司 | Starch composition for latex of cotton yarn dipped glove and application of starch composition |
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| CN113215830A (en) * | 2021-04-22 | 2021-08-06 | 杭州纸友科技有限公司 | Starch composition for latex of cotton yarn dipped glove and application of starch composition |
| CN113215830B (en) * | 2021-04-22 | 2022-07-19 | 杭州纸友科技有限公司 | Starch composition for latex of cotton yarn dipped gloves and application of starch composition |
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